Hair color-rinse concentrate



Patented June 23, 1953 HAIR COLOR-RINSE CONCENTRATE Marion J. Den Beste, St. Paul, Minn., assignor to Rayette, Inc., a corporation of Minnesota N Drawing. Application November 30, 1949,

Serial No. 130,369

Claims. 1

This invention relates to a hair rinse and particularly to a hair treating liquid containing coloring materials for the hair in combination with emollients capable of controlling the intensity and rate of coloring of the hair so that a smooth and uniform pre-selected tone may be imparted thereto.

In order to impart an even pre-selected color tone to the hair it is essential that a pre-determined quantity of a definite color be applied and that such color be completely and homogeneously distributed in the liquid medium prior to application to the hair.

The hair rinse composition of my invention is a stable, homogeneous, substantially completely dissolved concentrate of hair rinse components capable of subsequent dilution prior to use to provide the requisite quantity of color ingredients homogeneously distributed throughout the diluted solution. In the concentrate form the components are substantially dissolved to a homogeneous solution and in the diluted state some of the components are homogeneously suspended as a colloidal dispersion in the aqueous diluent medium.

In accordance with the preferred embodiment of my invention essentially water-soluble dyes are controllably and evenly applied to the hair by use in combination with an emollient oleaginous substance, essentially insoluble in water, which preferentially coats and conditions the hair and in which the dye or color has reduced solubility, so that the rate of penetration therethrough to the hair by the color is controlled, resulting in color ing of the hair an even tone.

My composition includes a color having a relatively high degree of water solubility together with an emollient having a substantial but relatively low degree of solubility for the color and having a preferential wetting effect upon the hair whereby to control the rate of passage of color therethrough to the hair.

My composition preferably has a controlled comparatively high viscosity to impart body to the concentrated liquid. The pH of the solution is controlled to that of optimum dye effectiveness.

To impart the desirable character of homogeneous solution in the concentrated form, a common solvent for the aqueous medium and for the substantially water insoluble emollient is used. Water soluble solvents of the character of low molecular weight non-toxic alcohols, acetone and other non-toxic water-soluble neutral organic solvents are used, of which the low molecular weight alcohols are preferred.

The composition will generally contain for pH control, acidifying acids or salts, preferably organic acids, t control the acidity requisite for the various dyes. The composition may further contain buffering salts.

The emollient component of the composition will preferentially coat the hair and control the coloring rate and distribution for even tone. The emollient has, either inherently or by compounding of other components therewith, polar characteristics in order that the emollient, upon dilution with water remains homogeneously suspended in the aqueous medium. The emollient is modified to have polar characteristics in order that the dye will slowly dissolve therein and penetrate therethrough to the hair.

My preferred emollient is a neutral oil of substantially high molecular weight containing polar groups such as one or more ether groups and hydroxy groups. Specifically my preferred emollient compounds are alkyl phenoxy alkanols of the type which may have one or more alkylene ether groups. Such compounds have the formula:

R on'hon wherein R is alkyl ranging from 1 to 12 carbon atoms preferably from 6 to 10 carbon atoms of the branched chain type, R is a lower alkylene such as methylene, ethylene, propylene or isopropylene, and a: is a whole integer from 1 to 5.

The positioning of substituents in the ring may be ortho, meta or para. Compounds such as piso-octyl phenoxy ethanol, p-di-iso amyl phenoxy di-ethoxy ethanol, di-iso-butylphenoxy ethanol, p-iso octyl phenoxy tetra ethoxy ethanol, o-iso hexyl phenoxy di-methoxy methanol. p-iso propyl phenoxy iso propanol are exemplary. These compounds are useful as emollients, are readily dissolved by a common solvent in water, and upon ultimate dilution will remain stably suspended in the aqueous medium, will preferentially wet the hair and will allow the dye to penetrate to the hair evenly.

The emollient is generally used in proportions of l to 10 parts by volume of the concentrate of which I prefer 4. to 6 parts.

The dye selected will vary with the color desired and is generally a, government certified non-toxic dye or mixture of dyes of the class whose components have substantial water solubility but also have a substantial but lower degree of solubility in the emollient. This property is generally exhibited by organic dyes having auxo-chrome groups and dyes such as the quinoline, monoazo, disazo, diphenylmethane, triphenylmethane, anthraquinone, xanthene, acridine, and indigoid dyes have been found to be useful herein. Other types of dyes having these characteristics will suggest themselves to one skilled in the art. The following table is exemplary of; specific dye types capable of use herewith:

Government approved types Color Class or type Iil idex Commercial Identification Quinolinc 801 D 6: yellow #10. Monoazo. 151 D. 6 G, orange #4 Do. 79 D & 0 red #5.

Do 165 D 6: 0 red #8. Diphenylmetliune 697 D & O violet #1. Triphenylmcthane 666 D & 0 green #1. Disazo 246 D & C black #1.

Do 234 D & C brown #1 Do. 252 D & 0 external red #13. Anthraquinonc. 073 v D & C' external violet #2. Xuntheno 768 DV 6; 0 red #22.

Do 778 D &'0 red #28.

Indigoid 1177 D & Gblue #6.

The dye may vary considerably in concentration and in concentrated 'form will generally range from .01 to 1 part of dye-by weight per hundred parts by weight of concentrate. It will be appreciated that Wide variation from these limits depending upon the type, intensity and tone of color desired, will be permissible.

As common solvents such as neutral watersoluble solvents asmethyl, ethyl,'propyl, isopropyl, n-butyl, isobutyl, secondary butyl and tertiary butyl alcohols, and-acetone are useful examples of which isopropyl alcohol is preferred as solvent. In the concentrated form the common solvent is variable with the quantity of emollient to be rendered soluble in the aqueous medium and will generally comprise to 70 volume parts per hundred volumes of concentrate and in the preferred range will vary from to 45.

The acid and buffers used may be any useful to control the pH and, of course, the pH will be that necessary for the particular dye and will be variable over a relatively wide pH range of 2 to 8. The acidity and buffering also has; an effect upon the stability and solubility ofthe components of a mix. Thus, for an acid dye, such as one of the types listed in the table above,-a preferred pH range would be 3.1 to 3.2 obtained by addition of an acid, preferably an organic acid such as citric acid, but various other organic acids such as the simple low molecular weight mono and di-basic aliphatic acids such as acetic and tartaric acid, would be useful. Various buffering salts such as sodium citrate, sodium carbonate, and the mono and di-basic alkali metal phosphates may be used to buffer the solution. The acid and buffers added will generally be sufficient to provide the optimum pH for the particular dye as recommended by'the manufacture for use of each dye and the buffer should be properly chosen with a view to maintaining stability in the presence of aqueous diluting mediums of characteristics which may vary, depending upon the particular water source.

As a thickening agent we prefer the water soluble gelatinous organic bodies such as the polyvinyl alcohols, the cellulose ethers and salts. Thus, we may use polyvinyl alcohol, methyl cellulose, or carboxy methyl cellulose or its alkali metal salts. The viscosity of the methyl cellulose varies with the degree of'methylation genera ally comprising 1 to 3 methoxyls per cellulose molecule. I have generally found on a hundred gallon basis of concentrate, 5 to 10 lbs. of medium viscosity methyl cellulose is satisfactory to impart requisite thickness thereto.

The following is a general base formula of the concentrate:

100 gallons Common solvent 25 to '70 gallons Thickening agent 5 to 10 lbs. Acid and buffering salts- To pH range of 2-8 Alkyl phenoxy alkanoL 1 to 10 gallons Color .01 to 1 lb.

Water Balance (to 100 gallons) The concentrate is formed by first wetting the thickening agent if methyl cellulose is used with the solvent and then agitating until it is well dispersed. Thereafter it is diluted with water until a smooth mixture is obtained. A solutiolf in a small amount of water of the buffering salt and acid is then added to the batch with agitation. The alkyl phenoxy alkanol is then added with agitation until all materials are. dis solved, and the solution is finally brought to volume, by addition of the total amount of water. The dye, and if desired, some perfume, are added with agitation until complete homogeneity is obtained. The, solution may finally be filtered to remove any solid particles. If desired the thickening agent may be dispersed in water in the first step with a moderate heat of to F. to enhance the rate. of solution. The concentrate is a substantially clear stable solution. The exact sequence of addition of materials is not critical, since they are'all substantially dissolved, except that a homogeneous solution may be obtained more rapidly by following the sequence given. The composition is apparently in the form of a complete solution; it is in fact homogeneous and no particles will settle, nor may they be-removed by filtration. However, the solution may be slightly cloudy, indicating that some of the components maybe in the colloidal sol state.

The concentrate as given above may be supplied to jobbers. or professional beauticians as such without the dye, and the dye may be subsequently added by the jobber, so that a single base stock solution would; have a wide usefulness for blending color therewith by choice at the site where it is to. be used. In use, the concentrate containing dye will be. diluted with water by addition to one part: of concentrate of from 30 to 45 parts of water. After dilution, the solution is broken, sincein the dilutedstate insuflicient common solvent is present to maintain the emollient in dissolved state. As noted above, this polar type emollient will naturally remain colloidally suspended as. a fine colloidal dispersion in water and will not separate. The thickening agent will also tend to enhance the emulsion stability.

When applied to the hair the emollient in the diluted solution acts to wet the hair fiber preferentially and the dye slowly penetrates therethrough to color the hair the preselected desired tint. After drying of the hair, the emollient remains as a coating upon the hair and protects the dyed hair-fiber, serves as a hair conditionin or grooming agent, and also serves to maintain whatever tint has been imparted thereto for a relatively longperiod of time. Thus, after tinting, subsequent accumulation of dust and dirt in the hair will not substantially affect the @910! Or brilliance of the tint.

The following are specific examples of useful concentrates:

Example I 100 gallons Isopropyl alcohol 35 gals. Methocel 7 lbs. Iso octyl phenoxy (ii-ethoxy ethanol 6.5 gals. Citric acid 32 lbs. Sodium citrate 6 lbs. Color, D & C orange #4 lb. Perfume lb. Water Balance (to make 100 gals.)

Example II 100 gallons Isopropyl alcohol 40 gals. Methocel (medium viscosity) 8% lbs. Sodium citrate 8%; lbs. Tartaric acid 35 lbs. Iso octyl phenoxy tetra ethoxy ethanol 6.2 gals Color, ext. D 8; C

brown #1 1 lb. Water Balance (to make 100 gals.)

Example III 100 gallons Isopropyl alcohol 40 gals. Methocel 8 lbs. Sodium citrate 30 lbs. Citric acid 31 lbs. Iso octyl phenoxy ethanol 6.4 gals. Perfume 2 lbs. D & C yellow #8 50 ml. Water Balance (to make 100 bals.)

(In this example the color added is lIlSllfilcient to dye the hair but will merely impart a sufiicient color to render the base product attractive. The desired dye and quantity thereof necessary for coloring hair is later selected and added just prior to use. Or such a clear base as in Example III may be used to dilute or extend a base mixture in which the dye is already dissolved, as in Example II.)

Either the concentrate containing the dye, or the base to which the dye is later added prior to dilution, may be used as desired. Color tints for dyeing the hair may be varied by blending of precolored concentrates when they are supplied with the dye in them. Thus, the present invention provides a, composition supplied as a stable homogeneous solution of concenerate containing a hair emollient and conditioner which serves to control the rate and quality (intensity) of tint applied thereto both as to color and evenness of application and to protect and condition the tinted hair after treatment.

Various modifications will occur to those skilled in the art. For example, other nontoxic dyes and hair emollients may be used to approximate the conditions of tinting set forth herein. It will be understood that the concentrate is homogeneous, but after dilution with water the dye will be substantially dissolved in the aqueous phase and will penetrate the emollient phase suspended therein at a controlled slow rate. It will be further understood that the emollient is applied to the hair to act as a protective and controlling agent while the dye slowly penetrates to the hair. The examples set forth herein are for purposes of illustrating the invention and are not to be construed as limiting thereof except as defined in the claims.

I claim:

1. Composition as defined in claim 6 wherein the said emollient oil is a mixture of several 6 to 10 carbon atom alkyl phenoxy poly ethoxy ethanols containing 1 to 5 ethoxy groups.

. ,2. Composition as defined in claim 6 wherein the emollient oil is p-di-iso butyl phenoxy ethanol.

3. Composition as defined in claim 6 wherein the emollient oil is p-di-iso butyl phenoxy diethoxy ethanol.

4 4. Composition as defined in claim 6 wherein the emollient oil is p-di-iso butyl phenoxy tetra ethoxy ethanol.

' 5. A concentrate capable upon subsequent dilution with 30 to 45 parts of water per part of concentrate, of forming a hair rinse comprising on a hundred gallon basis,

Common solvent, consisting essentially of a lower aliphatic monohydric alcohol 25 to 70 gallons Thickening agent, selected from the group consisting of polyvinyl alcohol and a water soluble cellulose ether 5 to 10 lbs. Acid and buffering salts To pH range of 2-8 6 to 10 carbon atom alkyl phenoxy ethyleneoxy ethanol having 0 to 4 ethyleneoxy groups- 1 to 10 gallons Non-toxic water soluble acid dye .01 to 1 lb. Water Balance (to gals) 6. A concentrate for tinting human hair by dilution thereof with water comprising a homogeneous aqueous solution of a non-toxic water soluble acid dye contained therein in quantity sufiicient to tint the hair upon dilution of the concentrate volume several times with water, said aqueous concentrate containing 1 to 10 parts by volume of a water insoluble emollient oil having the formula:

(OR/LOB wherein R is alkyl ranging from 6 to 10 carbon atoms, R is ethylene, and a: is a whole integer from 1 to 5, said composition further containing a small quantity of a lower water soluble monohydric aliphatic alcohol in quantity adjusted to dissolve the water insoluble emollient oil to form a homogeneous solution thereof in the concentrate, said concentrate being adapted upon subsequent further dilution with water to form a stable emulsion of said emollient oil in the aqueous dye solution for direct use as a hair tinting rinse.

7. The composition defined in claim 6 wherein the solution is buifered in the pH range of 2 to 8.

8. The composition as defined in claim 7, further containing 5 to 10 pounds of a thickening agent selected from the group consisting of polyvinyl alcohol and a water soluble cellulose ether per 100 gallons of concentrate.

9. A homogeneous concentrate adapted for use in the tinting of human hair, having the .follow- .ing formula onv the basis'of approximately; 100

gallons of the concentrate:

100- gallons Lower aliphatic monohydric alcohol 25- to70ga llons Thickening agent, selected from the group consisting of polyvinyl a1- cohol and a water soluble cellulose ether 5 to lo lbs. Organic acids and buffering salts To; pH range of2-8 6 to 10 carbon atom alkyl p h e n o x y ethyleneoxy ethanol having to '4 ethyleneoxy groups '1 to'IO gallons Non-toxic water soluble acid dye .01 to 1 lb. Water Balance to make .100 gallons 10. A homogeneous concentrate adapted 'for use in the tinting of human hair comprising, on a 100-gallon basis of concentrate, 25 to 70 gallons of isopropyl alcohol, 5 to pounds of methyl cellulose, sufiicient buffering agent toadjust the pH to the range of approximately 3.1 to 3.2, 4 to 6 gallons of alkyl phenoxy ethyleneoxy' ethanol having 0 to 4 ethylene oxy groups, the

alkyl group containingfrom 6' to 10 carbon atoms,

.01 to 1 lb. of water soluble acid dye. and water in quantity suflicient'to. bring the total volume of the concentrate to approximately gallons.

Goldsmith: (Non-Ionic Surface Active Agents," Chemical Industries, March 1943, pages 326 to 328.

Sisley: "Nonionic Compounds American Dyestuff Reporter, July 11, 1949, pages 513 to 521.

Borghetty: AuxiliaryProducts in Dyeing, American Dyestuff Reporter, November 29, 1948, pages P785 to 787.- 1 

6. A CONCENTRATE FOR TINTING HUMAN HAIR BY DILUTION THEREOF WITH WATER COMPRISING A HOMOGENEOUS AQUEOUS SOLUTION OF NON-TOXIC WATER SOLUBLE ACID DYE CONTAINED THEREIN IN QUANTITY SUFFICIENT TO TINT THE HAIR UPON DILUTION OF THE CONCENTRATE VOLUME SEVERAL TIMES WITH WATER, SAID AQUEOUS CONCENTRATE CONTAINING 1 TO 10 PARTS BY VOLUME OF A WATER INSOLUBLE EMOLLIENT OIL HAVING THE FORMULA: 